US4141806A - Bulk photo polymerization process for esters of acrylic and methacrylic acids - Google Patents

Bulk photo polymerization process for esters of acrylic and methacrylic acids Download PDF

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US4141806A
US4141806A US05/756,060 US75606077A US4141806A US 4141806 A US4141806 A US 4141806A US 75606077 A US75606077 A US 75606077A US 4141806 A US4141806 A US 4141806A
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Berthold Keggenhoff
Hans J. Rosenkranz
Hans Rudolph
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

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  • the subject of the present invention is a process for the photoinitiated bulk polymerisation of ethylenically unsaturated monomers.
  • the photoinitiated polymerisation of ethylenically unsaturated monomers is one of the oldest polymerisation processes and is frequently employed for the investigation of polymerisation mechanisms. In such polymerisation experiments, the reaction is in general discontinued after a conversion of a few per cent. An investigation of the behaviour at high conversion has only rarely been carried out.
  • the use of photopolymerisation has extended almost exclusively to photocrosslinking systems, such as photoprint plates and photocuring lacquer systems (compare H. Barzinsky, Chem. Ztg. 1972, page 545).
  • the only industrially utilised photopolymerisations of non-crosslinked systems which are taken to high conversions are confined to aqueous solutions of water-soluble monomers DT-AS No.
  • the polymerisation of ethylenically unsaturated monomers is in general effected with the aid of radical initiators, in most cases peroxidic radical initiators, which decompose thermally.
  • radical initiators in most cases peroxidic radical initiators, which decompose thermally.
  • the bulk polymerisation process is distinguished by the purity of the products obtained, and their economical manufacture. Disadvantages are the high exothermicity, the difficulties in removing the heat of reaction from the generally very viscous reaction mixture, and frequently a very broad molecular weight distribution of the products obtained.
  • DT-OS German Offenlegungsschriften
  • Nos. 1,965,740 and 2,304,847 describe a process for the thermally initiated bulk polymerisation of monomer mixtures containing acrylic esters, which is characterised in that the reaction mixture is polymerised, in a first stage, in the presence of a radical initiator which decomposes below 100° C., and the resulting 60-70% strength polymer syrup is mixed with a second radical initiator, which decomposes above 100° C., and is finally polymerised, to conversions above 90%, at a higher temperature.
  • the bulk polymerisation of acrylic esters cannot be taken to conversions of above 90% of a single thermally decomposing radical initiator is used. This is because if only one initiator, which decomposes at a low temperature, is used, the polymerisation only continues very slowly above 60-70% conversion and finally comes to a stop. The isolation of the pure polymer then requires expensive removal of the considerable residual amount of monomer, which is generally effected by evaporation.
  • the temperature of the reaction mixture in the first stage can be chosen within a wide range, below its boiling point, in accordance with the polymerisation behaviour of the monomers.
  • the polymerisation in the first stage can be carried out, for example, at or, if appropriate, even below room temperature.
  • the temperature in the first reaction stage can be 70-80° C. or more below the boiling point of the reaction mixture. In many cases, a reaction temperature of 50-100° C. has proved appropriate.
  • the process furthermore has the advantage of a relatively low activation energy of the polymerisation, which is about 4 kcal/mol. This makes the reaction thermally easily controllable and virtually excludes too vigorous a course due to adventitious temperature fluctuations of the system.
  • the bulk polymerisation process according to the invention is therefore relatively safe and can easily be handled industrially, particularly since the storage and handling of the photoinitiators also present no problems.
  • the rate of polymerisation can be controlled in a simple manner by varying the intensity of the UV light with which the mixture is irradiated.
  • the present invention provides a process for the bulk polymerisation of ethylenically unsaturated monomers, comprising polymerisation of the monomer in the presence of from 0 to 10% by weight of a photoinitiator by irradiation with UV light
  • the process of the present invention is advantageously applied to a monomer mixture which comprises esters of acrylic acid and methacrylic acid with aliphatic alcohols.
  • a particularly valuable process of the present invention comprises polymerisation of a monomer mixture of the following composition:
  • Copolymers produced by this process can be used, if appropriate after admixture of pigments and suitable crosslinking agents, that is to say substances which react with the functional groups of the monomers (C) to produce crosslinking, as lacquers for lacquering of, for example, domestic equipment, automotive components and machine components, or other metal articles.
  • suitable crosslinking agents that is to say substances which react with the functional groups of the monomers (C) to produce crosslinking
  • lacquers for lacquering of, for example, domestic equipment, automotive components and machine components, or other metal articles for this purpose they can be applied, dissolved in suitable solvents, by brushing or spraying, or can also be applied solvent-free in accordance with the methods of fluidised bed sintering or flame sintering, or the electrostatic powder spraying process.
  • the polymers can also be used as binding components in polymer blends, for example polyamide/polyolefine blends or polystyrene/polycarbonate blends.
  • the present invention provides a polymer when obtained by process of the present invention.
  • Suitable ethylenically unsaturated monomers with which the process according to the invention can be carried out are, for example, aliphatic, cycloaliphatic, aromatic and heterocyclic olefines and vinyl compounds, as well as their halogen derivatives and nitro derivatives, unsaturated alcohols, their ethers, esters and thioethers, as well as the corresponding sulphoxides and sulphones, unsaturated ketones, aldehydes and amines, unsaturated carboxylic acids, their amides, nitriles, anhydrides, esters and chlorides, vinyl-substituted inorganic acids and their derivatives, conjugated and non-conjugated dienes and polyenes, and other unsaturated compounds with olefinic double bonds, as well as mixtures of the said monomers.
  • Styrene Styrene, ⁇ -methylstyrene, chlorostyrene, bromostyrene and nitrostyrene.
  • the polymerisation recipes can furthermore contain customary additives, such as stabilisers and flameproofing agents and regulators, such as mercaptans or halogen compounds.
  • customary additives such as stabilisers and flameproofing agents and regulators, such as mercaptans or halogen compounds.
  • the initiation of the polymerisation is effected, in the process according to the invention, by irradiation with light.
  • This can be carried out without photoinitiators or, preferably, with photoinitiators in amounts of 0.001 to 10% by weight of the amount of monomer; 0.05-0.5% of photoinitiator are employed particularly preferentially.
  • Photoinitiators in the sense of the invention are all substances which, under the influence of light of suitable wavelength, produce radicals or ions which in turn are capable of initiating polymerisation reactions.
  • photoinitiators examples include benzoin and benzoin derivatives of the general formula I ##STR1## wherein R 1 denotes --O--Y or --S--Y and
  • Y denotes hydrogen, trimethylsilyl, C 1 -C 18 -alkyl
  • R 2 denotes hydrogen, C 1 -C 18 -alkyl, C 6 -C 15 -aryl, C 7 -C 15 -aralkyl, carboxyl or CH 2 --O--R' and R' is hydrogen or the acid radical of a carboxylic acid or of a sulphonic acid and
  • R 3 and R 4 denote hydrogen, C 1 -C 4 -alkyl, halogen, such as F, Cl, Br and I or --O--R" and
  • R" denotes C 1 -C 18 -alkyl
  • R 1 denotes CH 2 --X, CH--X 2 or CX 3 ,
  • R 2 denotes H, CH 3 , CH 2 --X, CH--X 2 or CX 3 and
  • X denotes chlorine, bromine or iodine.
  • the process can be carried out in various ways, and in particular both discontinuously and continuously. It is also possible to carry out one process stage continuously and the other discontinuously.
  • the first stage is suitably carried out in stirred vessels with heating and cooling equipment.
  • the lamps used for irradiation are built into the reaction vessels, as immersed lamps, or surround the reaction vessel from the outside, as a ring of lamps; in the latter case, the reaction vessel suitably consists of glass, quartz or some other material which transmits the UV light used.
  • the monomer mixture which contains the photoinitiator and, if appropriate, further additives, is fed into the reaction vessel as a constant stream and at the same time a corresponding amount of partially polymerised mixture is expelled from the reactor and transferred to the second stage.
  • the high viscosity of the completely converted reaction mixture must particularly be taken into account.
  • the process is carried out in dishes which are heated from the bottom face whilst they are irradiated with light from the top face, which is closed with a glass lid.
  • special mixers or extruders with an external glass wall can be used, so that the light which initiates the polymerisation can be radiated into the apparatus from outside. It is, however, also possible to use apparatuses such as are described in DT-AS No. 2,050,988 and German Offenlegungsschrift No. 2,009,748 that is to say the prepolymer can be spread, in a sufficiently thin layer, on heated flow belts and be finally polymerised on these by irradiation.
  • Light sources which can be used in both stages of the process according to the invention are mercury vapour lamps, fluorescent tubes, xenon lamps, carbon arc lamps or other lamps which emit light of a suitable wavelength. It is preferred to use so-called superactinic fluorescent tubes, which have a radiation maximum at a wavelength of 360 nm.
  • the percentage data are always % by weight.
  • the molecular heterogeneity H n is defined as follows:
  • Mn number-average molecular weight
  • a reaction mixture of 480 g of styrene, 390 g of butyl acrylate, 130 g of acrylic acid, 15 g of t-dodecylmercaptan and 1 g of benzoin isopropyl ether is exposed to light in a thermostatically controlled vessel having an immersed lamp (fluorescent tube of 6 W, radiation maximum 360 mn) at 73° C. for 71/4 hours.
  • the polymer conversion in this first stage is 65.5%.
  • the mixture is then filled into a dish closed with a glass lid and is exposed to light from a similar fluorescent tube, whilst being heated to 135° C.
  • the polymerisation is taken to a conversion of 93.5%.
  • the gel chromatography of the polymer in tetrahydrofurane gives a molecular weight distribution corresponding to the Schulz-Flory distribution (see FIG. 1)
  • the relative concentration (ordinate axis) is shown in relation to the molecular weight (abscissa axis).
  • the molecular weight is here quoted indirectly in so-called counts, which correspond to the individual fractions.
  • the weight average molecular weight M w is 23,900 and the heterogeneity H n is 1.21.
  • the polymer has an acid number of 110.
  • a polymer of the same composition manufactured in accordance with the instructions of DOS (German Published Specification) No. 1,304,847 has a heterogeneity H n of 1.94 and a non-uniform molecular weight distribution which exhibits subsidiary maxima.
  • a reaction mixture of 900 g of methyl methacrylate, 100 g of methacrylic acid, 20 g of t-dodecylmercaptan and 2 g of benzoin isopropyl ether is polymerised analogously to Example 1.
  • Second stage temperature 105° C., illumination time 2 hours, conversion 96.1%.
  • a reaction mixture of 600 g of methyl methacrylate, 300 g of butyl acrylate, 100 g of hydroxypropyl methacrylate, 12 g of t-dodecylmercaptan and 1 g of benzoin isopropyl ether is polymerised analogously to Example 1.
  • Second stage temperature 120° C., illumination time 2 hours, conversion 94.4%.
  • a reaction mixture of 450 g of styrene, 400 g of butyl acrylate, 150 g of glycidyl methacrylate, 10 g of t-dodecylmercaptan and 3 g of benzoin isopropyl ether is polymerised analogously to Example 1.
  • First stage temperature 82° C., illumination time 10 hours, conversion 74.1%.
  • Second stage temperature 120° C., illumination time 2 hours, conversion 95.4%.
  • a reaction mixture of 400 g of methyl methacrylate, 500 g of butyl acrylate, 50 g of maleic anhydride, 10 g of t-dodecylmercaptan and 2 g of benzoin isopropyl ether is polymerised analogously to Example 1.
  • First stage temperature 87° C., illumination time 105 minutes, conversion 63.0%.
  • Second stage temperature 121° C., illumination time 120 minutes, conversion 96.3%.
  • a reaction mixture of 600 g of methyl methacrylate, 300 g of butyl acrylate, 50 g of acrylic acid, 50 g of acrylamide 20 g of t-dodecylmercaptan and 0.5 g of benzoin isopropyl ether is polymerised analogously to Example 1.
  • First stage temperature 98° C., illumination time 75 minutes, conversion 71.0%.
  • Second stage temperature 121° C., illumination time 120 minutes, conversion 92.8%.
  • a reaction mixture of 400 g of methyl methacrylate, 400 g of ethyl acrylate, 200 g of N,N-dimethylaminoethyl methacrylate, 15 g of t-dodecylmercaptan and 1 g of benzoin isopropyl ether is polymerised analogously to Example 1.
  • First stage temperature 84° C., illumination time 2 hours 10 minutes, conversion 64.3%.
  • Second stage temperature 120° C., illumination time 2 hours, conversion 96.6%.
  • a reaction mixture of 1,200 g of styrene, 975 g of butyl acrylate, 325 g of acrylic acid, 37.5 g of t-dodecylmercaptan and 2.5 g of benzoin isopropyl ether is illuminated for 4 hours at 80° C. in a stirred glass vessel equipped with internal heating and three symmetrically externally mounted fluorescent tubes (each 40 W, radiation maximum 360 nm).
  • the polymer conversion in this first stage is 62%.
  • the batch is then heated to 130° C. in the same vessel and illuminated for a further 11/2 hours.
  • the final conversion is 91.2%.
  • the molecular weight distribution determined by gel chromatography in tetrahydrofurane, corresponds to the Schulz-Flory distribution, the weight average molecular weight M w is 17,600 and the heterogeneity H n is 1.03.
  • a reaction mixture of 1,050 g of styrene, 637.5 g of butyl acrylate, 825 g of hydroxyethyl methacrylate, 26.3 g of acrylic acid, 75 g of t-dodecylmercaptan and 7.5 g of benzoin isopropyl ether is illuminated in the same stirred vessel as in Example 8, for 31/2 hours at 82° C., by means of four symmetrically externally mounted fluorescent tubes (each 25 W, radiation maximum 360 nm).
  • the polymer conversion in this first stage is 73.1%.
  • the temperature is then raised to 120° C., and the mixture is illuminated for a further 95 minutes.
  • the final conversion is 96.5%.
  • the molecular weight distribution determined by gel chromatography in tetrahydrofurane corresponds to the Schulz-Flory distribution.
  • the weight average molecular weight M w is 14,950 and the heterogeneity H n is 1.04.
  • the polymer has an OH number of 130.
  • a reaction mixture of 5,760 g of styrene, 4,440 g of butyl acrylate, 1,800 g of acrylic acid, 180 g of t-dodecylmercaptan and 12 g of benzoin isopropyl ether is photopolymerised continuously.
  • Two stirred glass vessels (3), (5) (shown in FIG. 2) each of about 3 l capacity, with heating and externally mounted fluorescent tubes, are used for the polymerisation.
  • Vessel (3) is temperature-controlled to 80° C. and vessel (5) to 140° C.
  • a total of 10 fluorescent tubes (radiation maximum 360 nm) having a total wattage of 470 W are arranged conjointly around both vessels.
  • the reaction mixture is fed from the stock tank (1) in a constant stream, by means of the pump (2), into the vessel (3), and after passing through the latter is passed on by the pump (4) into the vessel (5), from where it leaves as the end product (see FIG. 2).
  • the throughput is 1.27 kg/hour, the polymer conversion on leaving vessel (3) is 48.0% and the final conversion is 92.3% on leaving vessel 5.
  • the molecular weight distribution determined by gel chromatography in tetrahydrofurane corresponds to the Schulz-Flory distribution.
  • the weight average molecular weight M w is 19,400 and the heterogeneity H n is 1.02.
  • the polymer has an acid number of 110.
  • a reaction mixture of 4,800 g of methyl methacrylate, 2,400 g of styrene, 3,600 g of butyl acrylate, 1,200 g of glycidyl methacrylate, 240 g of t-dodecylmercaptan and 24 g of benzoin isopropyl ether is polymerised continuously as in Example 10.
  • the molecular weight distribution (determined in THF) shows no subsidiary maxima.
US05/756,060 1976-01-07 1977-01-03 Bulk photo polymerization process for esters of acrylic and methacrylic acids Expired - Lifetime US4141806A (en)

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DE2600318 1976-01-07
DE2600318A DE2600318C3 (de) 1976-01-07 1976-01-07 Verfahren zur Herstellung von Copolymerisaten

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JP (1) JPS5285275A (fr)
BE (1) BE850135A (fr)
CA (1) CA1072046A (fr)
CH (1) CH628650A5 (fr)
DE (1) DE2600318C3 (fr)
FR (1) FR2337736A1 (fr)
GB (1) GB1511821A (fr)
NL (1) NL7700088A (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4260465A (en) * 1980-01-04 1981-04-07 Stauffer Chemical Company Photopolymerizable composition stabilized with epoxide compounds and process
US4338172A (en) * 1977-02-18 1982-07-06 Stauffer Chemical Company Photopolymerizable composition stabilized with epoxide compounds and process
US4459192A (en) * 1977-05-16 1984-07-10 Stauffer Chemical Company Photopolymerizable composition stabilized with epoxide compounds and process
US4529787A (en) * 1982-06-15 1985-07-16 S. C. Johnson & Son, Inc. Bulk polymerization process for preparing high solids and uniform copolymers
US4530746A (en) * 1982-05-24 1985-07-23 Hitachi, Ltd. Photosensitive resin composition
US4546160A (en) * 1984-02-29 1985-10-08 S. C. Johnson & Son, Inc. Bulk polymerization process for preparing high solids and uniform copolymers
US4843134A (en) * 1984-03-28 1989-06-27 Minnesota Mining And Manufacturing Company Acrylate pressure-sensitive adhesives containing insolubles
US5026740A (en) * 1985-01-28 1991-06-25 Fratelli Lamberti S.P.A. Sulphurated derivatives of aromatic-aliphatic and aliphatic ketones as polymerization photoinitiators
US5053448A (en) * 1989-07-21 1991-10-01 S. C. Johnson & Son, Inc. Polymeric thickener and methods of producing the same
US5147901A (en) * 1982-10-01 1992-09-15 Ciba-Geigy Corporation Propionphenone derivatives as photoinitiators for photopolymerization
US5275914A (en) * 1992-07-31 1994-01-04 Polaroid Corporation Laminar thermal imaging medium comprising an image-forming layer and two adhesive layers
US5514525A (en) * 1993-09-23 1996-05-07 Polaroid Corporation Method of preparing a laminar thermal imaging medium
US5879759A (en) * 1997-12-22 1999-03-09 Adhesives Research, Inc. Two-step method for the production of pressure sensitive adhesive by radiation curing
US6124409A (en) * 1991-07-01 2000-09-26 Xerox Corporation Processes for preparing copolymers
US6448339B1 (en) 1997-05-13 2002-09-10 Soken Chemical & Engineering Co., Ltd. Adhesive composition
EP1624001A1 (fr) * 2003-05-09 2006-02-08 Taiyo Ink Manufacturing Co. Ltd Composition a jet d'encre photodurcissable/thermodurcissable et carte imprimee utilisant celle-ci
EP2398522B1 (fr) 2009-02-20 2017-01-11 Boston Scientific Scimed, Inc. Revêtement hydrophile qui réduit le développement de particule sur un poly (ester-bloc-amide) à liaison ester

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2348227A1 (fr) 1976-04-14 1977-11-10 Rhone Poulenc Ind Perfectionnement aux procedes de preparation de polymeres acryliques hydrosolubles par photopolymerisation
DE3902536A1 (de) * 1989-01-28 1990-08-16 Akzo Gmbh Sterisch stabilisierte waessrige polymer-dispersionen
KR100385728B1 (ko) * 2000-11-08 2003-05-27 주식회사 엘지화학 내충격성과 착색성이 우수한 열가소성 수지 조성물 및 그제조 방법

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US3666645A (en) * 1967-06-01 1972-05-30 Neutron Products Inc Multistage polymerization process with independently adjustable radiation sources
GB1310729A (en) 1969-10-22 1973-03-21 Rhone Progil Process for preparing water-soluble acrylic polymers and copoly mers
US3753958A (en) * 1969-12-31 1973-08-21 Bayer Ag Pulverisable acrylate resins
GB1332247A (en) 1970-03-03 1973-10-03 Basf Ag Manufacture of watersoluble polymers
US3879357A (en) * 1973-02-01 1975-04-22 Bayer Ag Pulverizable acrylic resins
US3929602A (en) * 1971-12-10 1975-12-30 Japan Atomic Energy Res Inst Low temperature irradiation of vitrifiable mixtures of unsaturated monomers

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CA925469A (en) * 1968-11-18 1973-05-01 Harada Susumu Process for producing polyaminesulfones
US3787382A (en) * 1972-02-16 1974-01-22 Gen Electric Photopolymerization of tetrafluoro-ethylene and polymer and products produced therefrom

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US3666645A (en) * 1967-06-01 1972-05-30 Neutron Products Inc Multistage polymerization process with independently adjustable radiation sources
GB1310729A (en) 1969-10-22 1973-03-21 Rhone Progil Process for preparing water-soluble acrylic polymers and copoly mers
US3753958A (en) * 1969-12-31 1973-08-21 Bayer Ag Pulverisable acrylate resins
GB1332247A (en) 1970-03-03 1973-10-03 Basf Ag Manufacture of watersoluble polymers
US3929602A (en) * 1971-12-10 1975-12-30 Japan Atomic Energy Res Inst Low temperature irradiation of vitrifiable mixtures of unsaturated monomers
US3879357A (en) * 1973-02-01 1975-04-22 Bayer Ag Pulverizable acrylic resins

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338172A (en) * 1977-02-18 1982-07-06 Stauffer Chemical Company Photopolymerizable composition stabilized with epoxide compounds and process
US4459192A (en) * 1977-05-16 1984-07-10 Stauffer Chemical Company Photopolymerizable composition stabilized with epoxide compounds and process
US4260465A (en) * 1980-01-04 1981-04-07 Stauffer Chemical Company Photopolymerizable composition stabilized with epoxide compounds and process
US4530746A (en) * 1982-05-24 1985-07-23 Hitachi, Ltd. Photosensitive resin composition
US4529787A (en) * 1982-06-15 1985-07-16 S. C. Johnson & Son, Inc. Bulk polymerization process for preparing high solids and uniform copolymers
US5147901A (en) * 1982-10-01 1992-09-15 Ciba-Geigy Corporation Propionphenone derivatives as photoinitiators for photopolymerization
US4546160A (en) * 1984-02-29 1985-10-08 S. C. Johnson & Son, Inc. Bulk polymerization process for preparing high solids and uniform copolymers
US4843134A (en) * 1984-03-28 1989-06-27 Minnesota Mining And Manufacturing Company Acrylate pressure-sensitive adhesives containing insolubles
US5026740A (en) * 1985-01-28 1991-06-25 Fratelli Lamberti S.P.A. Sulphurated derivatives of aromatic-aliphatic and aliphatic ketones as polymerization photoinitiators
US5053448A (en) * 1989-07-21 1991-10-01 S. C. Johnson & Son, Inc. Polymeric thickener and methods of producing the same
US6124409A (en) * 1991-07-01 2000-09-26 Xerox Corporation Processes for preparing copolymers
US5387490A (en) * 1992-07-31 1995-02-07 Polaroid Corporation Method of preparing a laminar thermal imaging medium
US5275914A (en) * 1992-07-31 1994-01-04 Polaroid Corporation Laminar thermal imaging medium comprising an image-forming layer and two adhesive layers
US5514525A (en) * 1993-09-23 1996-05-07 Polaroid Corporation Method of preparing a laminar thermal imaging medium
US5552259A (en) * 1993-09-23 1996-09-03 Polaroid Corporation Adhesive composition, and imaging medium comprising this adhesive composition
US6448339B1 (en) 1997-05-13 2002-09-10 Soken Chemical & Engineering Co., Ltd. Adhesive composition
US5879759A (en) * 1997-12-22 1999-03-09 Adhesives Research, Inc. Two-step method for the production of pressure sensitive adhesive by radiation curing
EP1624001A1 (fr) * 2003-05-09 2006-02-08 Taiyo Ink Manufacturing Co. Ltd Composition a jet d'encre photodurcissable/thermodurcissable et carte imprimee utilisant celle-ci
US20060058412A1 (en) * 2003-05-09 2006-03-16 Taiyo Ink Mfg. Co., Ltd. Photocurable and thermosetting composition for ink jet system and printed circuit boards made by use thereof
EP1624001A4 (fr) * 2003-05-09 2006-08-02 Taiyo Ink Mfg Co Ltd Composition a jet d'encre photodurcissable/thermodurcissable et carte imprimee utilisant celle-ci
US7462653B2 (en) 2003-05-09 2008-12-09 Taiyo Ink Manufacturing Co., Ltd. Photocurable and thermosetting composition for ink jet system and printed circuit boards made by use thereof
EP2398522B1 (fr) 2009-02-20 2017-01-11 Boston Scientific Scimed, Inc. Revêtement hydrophile qui réduit le développement de particule sur un poly (ester-bloc-amide) à liaison ester

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FR2337736B1 (fr) 1980-07-25
NL7700088A (nl) 1977-07-11
GB1511821A (en) 1978-05-24
FR2337736A1 (fr) 1977-08-05
BE850135A (fr) 1977-07-06
CH628650A5 (de) 1982-03-15
JPS5285275A (en) 1977-07-15
DE2600318C3 (de) 1982-04-08
DE2600318A1 (de) 1977-07-21
DE2600318B2 (de) 1981-06-04
CA1072046A (fr) 1980-02-19

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